JPH0625546A - Monoazo dye and mixture comprising the same - Google Patents

Abstract

PURPOSE:To obtain a new compound, assuming a red color, excellent in buildup properties, exhaustion characteristics and color fastness to light and useful for dyeing polyester fiber, etc., such as automotive cover fabrics, etc. CONSTITUTION:The compound of formula I [X is methyl, chlorine or bromine; R<1> is ethyl, n-propyl, n-butyl, etc.; R<2> is (1-4C alkoxy-substituted)2-4C alkyl, allyl, phenyl, acetyl or propionyl; R<3> is H, acetyl or propionyl], e.g. a compound of formula II. Furthermore, this compound of formula I is obtained by reacting a compound of formula III (Hal<1> and Hal<2> are chlorine or bromine) with cyanide ions of formula IV.

Description

Detailed Description of the Invention

[0001]

The present invention relates to monoazo dyes, mixtures containing monoazo dyes, a process for their preparation and their use for dyeing hydrophobic synthetic materials.

[0002]

Dyes similar to the dyes according to the invention have already been proposed.
It is disclosed in European Patent Application No. 43,795. However, they have drawbacks in practical applications, especially with regard to build-up and exhaust properties. As a result, for example, high color depths cannot be achieved and the effluent is relatively heavily contaminated. Moreover, their relatively high temperature sensitivity easily causes variations in color depth with variations in dyeing temperature.

[0003]

It is an object of the present invention to provide a dye having improved properties, in view of the dye of EP-A-43,795.

[0004]

The present invention is of general formula I

[0005]

[Chemical 5] [Wherein X is methyl, chlorine or bromine, and R ¹ is ethyl, n-propyl, i-propyl, n-butyl or i.
-Butyl, R ² is (C ₁ -C ₆ ) -alkyl,
(C ₁ -C ₄ ) -alkoxy substituted linear (C ₂ -C
₄₎ - alkyl, allyl, phenyl, acetyl or propionyl and R ³ is hydrogen, acetyl or propionyl. ] It is related with the monoazo dye represented.

(C ₁ -C ₆ ) -Alkyl as R ² can be linear or branched and, for example,
Methyl, ethyl, n-propyl, i-propyl, n-butyl, s-butyl, i-butyl, n-pentyl, 3-methylbutyl, n-hexyl or 2-ethylbutyl.

Examples of (C ₁ -C ₄ ) -alkoxy substituted linear (C ₂ -C ₄ ) -alkyl are 2-methoxyethyl, 2-ethoxyethyl, 2-n-propoxyethyl,
2-i-propoxyethyl, 2-n-butoxyethyl,
2-i-butoxyethyl, 4-methoxybutyl or 4
-Ethoxybutyl.

In the general formula I, X is preferably bromine and especially chlorine. R ¹ is preferably ethyl, n-propyl or i-propyl. R ² is preferably (C ₁ -C ₄ ) -alkyl, 2-methoxyethyl, 2-
Ethoxyethyl or allyl. R ³ is preferably hydrogen. Preferred dyes of the general formula I are those wherein X and R ¹ to R ³ are preferred substituents.

The present invention is of general formula I

[0010]

[Chemical 6] [Wherein X is methyl, chlorine or bromine, R ¹ is methyl, ethyl, n-propyl, i-propyl, n-butyl or i-butyl, and R ² is (C ₁ -C ₆ ) -alkyl. , (C ₁ -C ₄ ) -alkoxy substituted linear (C
₂ -C ₄₎ - alkyl, allyl, phenyl, is and R ³ is acetyl or propionyl hydrogen, acetyl or propionyl. ] It also relates to a mixture of at least two monoazo dyes of the formula

A preferred mixture according to the invention is X,
R ¹ , R ² and R ³ are preferred groups, or R
Included are monoazo dyes of general formula I in which ¹ is methyl and X, R ² and R ³ are preferred groups.

In a particularly preferred mixture according to the invention, the monoazo dyes of the general formula I differ only in the meaning of the radical R ¹ . In the dye mixtures according to the invention, the proportions of the various dyestuffs of the general formula I can be varied within a relatively wide range, and the dyestuffs can be in the form of crystalline mixtures or else wholly or partly mixed crystalline crystals. Can exist in the form of. Generally, the minimum weight% of one component is 10% and the maximum weight% is 90%. In the case of dye mixtures containing only two dyes of the general formula I, a weight ratio of 70:30 to 30:70 is preferred, i.e. the weight% of one dye is 30 to 70%.

In a special embodiment of the invention, the dyestuffs of the general formula I or their mixtures are C.I. I. Colored with Solvent Orange 63 or similar dyes.

A further particular embodiment of the present invention is used for dyeing one or more dyestuffs of the general formula I and usually polyester fibers or polyester fiber materials for automobile cover fabrics. Mixtures with one or more dyes. Dyes for dyeing automobile cover fabrics are, in particular, azo, disazo, anthraquinone, nitro, naphthalimide and terephthalimide dyes. Particularly preferred dyes of this type are the color index dyes Yellow 23, Yellow 42, Yellow 51, Yellow 59, Yellow 71 and Yellow 8.
6, yellow 108, yellow 122, yellow 16
3, Yellow 182, Orange (Orange) 29, Orange 30, Orange 32, Orange 41, Orange 45, Orange 61, Orange 73, Red 60, Red 86, Red 91, Red 92, Red 127, Red 134, Red 138, Red 159, Red 167,
Red 191, Red 202, Red 258, Red 2
79, Red 284, Red 302, Red 323, Blue 27, Blue 54, Blue 56, Blue 6
0, blue 77, blue 79: 1, blue 87, blue 266, blue 333, violet 27, violet 28, violet 57 and violet 95.

The weight ratios of the dyestuffs of the general formula I or their mixtures as well as the abovementioned dyestuffs are not critical and depend on the desired shade. The dyestuffs according to the invention of the general formula I preferably have the general formula II

[0016]

[Chemical 7] Wherein Hal ¹ and Hal ² are, independently of one another, chlorine or preferably bromine and R ¹ , R ² , R ³
And X are as defined above. ] The compound represented by is subjected to a nucleophilic exchange reaction, and the nucleophile used in that case is a cyanide ion.

[0017]

[Chemical 8] Is manufactured by. H which is chlorine or bromine
This reaction, in which al is exchanged for CN, is preferably carried out in DE-A-1,809,920, DE-A-1,809,92.
No. 1, British Patent No. 1,184,825, German Patent Application Publication No. 1,544,563, German Patent Application Publication No. 2,310,74.
Publication No. 5, German Patent Application Publication No. 2,45
6,495, German Federal Patent Application Publication No. 2,610,675, German Federal Patent Application Publication No. 2,724,116, German Federal Patent Application Publication No. 2,724,117. German Patent Application Publication No. 2,834,137, German Patent Application Publication No. 2,341,109,
It is carried out by the method described in U.S. Pat. No. 3,821,295, German Patent Application Publication No. 2,715,034 or German Patent Application Publication No. 2,134,896.

The compounds of general formula II are preferably prepared by methods known to those skilled in the art, preferably of general formula III

[0019]

[Chemical 9] [Wherein X and Hal ¹ and Hal ² are as defined above. ] The amine represented by the formula

[0020]

[Chemical 10] [Wherein R ¹ , R ² and R ³ are as defined above. ] It manufactures by coupling with the amine represented by these.

The compounds of general formulas III and IV are known and can be prepared by methods known to those skilled in the art. The dyes of the general formula I according to the invention or the mixtures according to the invention are compounded before dyeing, i.e. they are in the presence of water and a dispersant in a suitable mill, for example a ball or sand mill. Ground in,
Then, if a powdered dye formulation is to be produced, it is then spray dried.

Examples of suitable dispersants are anionic or nonionic dispersants, which can also be used together. Examples of anionic dispersants are condensation products of aromatic sulfonic acids with formaldehyde, in particular condensation products of alkylnaphthalene sulfonic acids with formaldehyde, substituted or unsubstituted phenols with formaldehyde and sodium bisulfite. Condensation products with, substituted or unsubstituted phenols, alkali metal salts of condensation products of naphthalene- or naphtholsulfonic acids with formaldehyde and sodium bisulfite, substituted or unsubstituted phenol sulfones Alkali metal salts of condensation products of acids with formaldehyde and urea and alkali metal salts of ligninsulfonic acid; alkyl- or alkylaryl sulfonates, and alkylaryl polyglycol ether sulfonates A.

Examples of nonionic dispersants or emulsifiers are compounds which can be alkylated with alkylene oxides, eg ethylene oxide or propylene oxide, eg
Reaction products with fatty alcohols, fatty amines, fatty acids, phenols, alkylphenols, arylalkylphenols, arylalkylarylphenols and carboxamides, for example addition products of 5 to 10 ethylene oxide units with (C ₈ -C ₁₀ ) -alkylphenols. is there.

The milling is carried out at a temperature of 10 to 90 ° C, preferably 30 to 60 ° C. If the separately prepared individual compounds are compounded together, it is advantageous to grind them together at temperatures above 30 ° C. At that time, the dye particles are
Mechanically powdered to the extent that an optimum specific surface area is achieved and dye settling is kept to a minimum. The particle size of the dye is generally 0.5 to 5μ, preferably about 1μ.

The dye mixtures according to the invention can be prepared in various ways, for example by mixing the individual dyes prepared separately, preferably the already incorporated individual dyes. To mix. This mixing step is carried out in a suitable mixer, such as a tumbling mixer or stirrer. However,
It is also possible to mix the individually formulated individual dyes by placing them in the dye liquor with stirring.

Furthermore, the dye mixtures according to the invention can preferably be prepared by blending the separately prepared mixing components together, ie by milling and / or spray drying together.

Furthermore, the dye mixtures according to the invention can preferably be prepared by mixing the dye precursors of the general formula II and then, as mentioned above, cyano-exchanging them together.

The composition of the mixture of dye precursors of the general formula II is selected so that the mixture according to the invention is formed. This step is followed by compounding, as described above. If it is desired to mix together the separately prepared dyes of the general formula I, it is advantageous to preheat them together. This treatment involves the addition of the individual dyestuffs of the general formula I together in water, optionally under pressure, from 50 to
It is characterized by heating at a temperature of 150 ° C., preferably 90 to 130 ° C. for half an hour to several hours, and then returning to the original state by cooling. This heating is advantageously carried out in the presence of one or more dispersants or organic solvents. Examples of such solvents are methanol, ethanol, dimethylformamide or dimethylsulfoxide, but preferably solvents having a low solubility in water, such as toluene, chlorobenzene, 1,2-dichlorobenzene or butyl acetate. . These solvents can be distilled off again after the heat treatment. However, these solvents can also be separated by filtration and subsequent washing of the mixture with water. This separation step may then be followed by blending the mixture.

Particularly preferably, the separately prepared dyestuffs of the invention of the general formula I are dissolved together in an organic solvent, solvent mixture or mineral acid before compounding and subsequently crystallized. And / or is precipitated, isolated by filtration, for example, and treated by removing solvent residues, for example by washing. Again, this treatment may be followed by compounding the mixture.

Preferred organic solvents are polar protic solvents such as dimethylformamide, dimethylsulfoxide or N-methylpyrrolidone. It is advantageous to completely dissolve the mixed components. In the case of poorly soluble mixed components, this can be achieved by increasing the amount of solvent, the dissolution temperature or the dissolution time. In order to save the solvent, the dissolution is preferably carried out at elevated temperature, using temperatures up to the boiling point of the individual solvent. In some cases
It is possible to raise the temperature further under pressure.

The dyes and dye mixtures according to the invention, either alone or in admixture with another disperse dye, are very suitable for dyeing and printing hydrophobic synthetic materials. Examples of suitable hydrophobic synthetic materials are secondary cellulose acetate, acellulose triacetate, polyamides and high molecular weight polyesters. Preferably, the dyes according to the invention are used for dyeing and printing materials made from high molecular weight polyesters, especially those based on polyethylene glycol terephthalate or blends thereof with natural fiber materials, or cellulose triacetate materials. .

The hydrophobic synthetic material can be present in the form of a sheet-like or filament-like structure and can be processed, for example, into threads or woven or knitted fibrous materials. The dyeing of the abovementioned fiber materials with the dyestuffs or dyestuff mixtures according to the invention can be carried out in a manner known per se, preferably from aqueous suspensions, optionally in the presence of carriers, by the exhaust method at 80 to about 110 ° C. Or 11 in a dyeing autoclave by high temperature (HT) method
It can be carried out at 0 to 140 ° C., as well as by the so-called heat fixing method in which the material is padded with a dye liquor and then fixed at about 80 to 230 ° C. The printing of the abovementioned materials is carried out in a manner known per se by incorporating the dyestuff or dyestuff mixture according to the invention into the printing paste and printing the material with it, optionally in the presence of a carrier, at a temperature of from 80 to 230 ° C. in a high-temperature steam. , Pressurized steam or dry heat. In this way, a very high color strength and very good general use fastness are obtained, for example fastness to dry heat fixing, washing, water and heat transfer fastness and especially very good light fastness. A brilliant bluish red dyeing which has is obtained.

The dyes and dye mixtures according to the invention are particularly well suited for dyeing and printing polyester fibers and polyester fiber materials for automobile cover fabrics. For this purpose, preference is given to using the abovementioned dyestuffs of the general formula I and mixtures thereof with one or more dyestuffs customarily used for dyeing automobile cover fabrics. In addition, the dyeing of car cover fabric,
It is preferably carried out in the presence of a UV absorber. Examples of suitable UV absorbers are those based on benzophenone and benzotriazole.

For more information on dyeing automotive cover fabrics, see
For example, Textilveredelung 20 (1985), No. 4, No. 126.
Page, 20 (1985), No. 11, page 356 and 23 (1988), No.
5, page 170.

The dyestuffs or dyestuff mixtures according to the invention are likewise suitable for dyeing the above-listed hydrophobic materials from organic solvents by the methods known therefor. In the dye liquors or printing pastes used in the above applications, the dyes or dye mixtures according to the invention should be present in a very finely divided form.

The fine dispersion of the dyestuffs is carried out in a manner known per se by suspending the as-synthesized dyestuffs together with a dispersant in a liquid medium, preferably water, and subjecting the mixture to the action of shear forces. The initially present dye particles are mechanically comminuted to the extent that an optimum specific surface area is achieved and dye settling is kept to a minimum. The particle size of the dye is generally 0.5 to 5 μm, preferably about 1 μm.

The dispersant used in the milling process can be nonionic or anionic. Examples of nonionic dispersants are the reaction products of alkylene oxides such as ethylene oxide or propylene oxide with compounds which can be alkylated such as fatty alcohols, fatty amines, fatty acids, phenols, alkylphenols and carboxamides. Examples of anionic dispersants are lignosulphonates, alkyl- or alkylaryl sulphonates or alkylaryl polyglycol ether sulphates.

The dye preparations thus obtained should be castable for most applications. Therefore, the dye and dispersant content is limited in these cases. Generally, the dispersion has a dye content of 50% by weight and about 25%.
Up to a dispersant content of up to. For economic reasons, the dye content in most cases does not fall below 15% by weight.

The dispersions may also be auxiliaries, such as those acting as oxidants, such as sodium m-nitrobenzenesulfonate or fungicides such as sodium o-.
Phenylphenolate and sodium pentachlorophenolate and especially so-called "acid donors", eg
Butyrolactone, monochloroacetamide, sodium chloroacetate, sodium dichloroacetate, sodium 3-chloropropionate, monoesters of sulfuric acid, such as lauryl sulphate, sulfuric acid esters of ethoxylated and propoxylated alcohols, such as butyl glycol sulphate. Can also be included.

The dye dispersions thus obtained can be used very advantageously in the production of printing pastes and dye liquors. The dispersion is particularly advantageous, for example, in a continuous process in which the dye concentration of the dye liquor must be kept constant by continuously metering the dye into the operating equipment.

Powder formulations are preferred for certain application areas. These powders contain dyes or mixtures of dyes, dispersants and further auxiliaries such as wetting and oxidizing agents, preservatives and dustproofing agents and the "acid donors" mentioned above.

A preferred method of preparing a powder dye preparation consists in removing the liquid from the above liquid dye dispersion, for example by vacuum drying, freeze drying, drying in a drum dryer, but preferably by spray drying.

For the preparation of the dye liquor, the required amount of dyestuff preparation prepared according to the above description is used in the dyeing medium, preferably water, with a bath ratio of 5: 1 to 50: 1 being obtained during dyeing. Dilute to a certain degree. Additionally, further dyeing auxiliaries, for example:
Dispersants, wetting agents and sticking aids are added to the liquid. The pH is adjusted to a value of 4-5, preferably 4,5, by adding organic and inorganic acids such as acetic acid, succinic acid, boric acid or phosphoric acid. PH obtained
Buffering and adding a sufficient amount of buffer system. An example of an advantageous buffer system is the acetic acid / sodium acetate system.

If it is desired to use the dyestuffs or dyestuff mixtures for printing textiles, the required amount of dyestuff preparation is added in a manner known per se to thickeners, such as alkali metal alginates, and optionally Further, an auxiliary agent such as a sticking accelerator, a wetting agent and an oxidizing agent is kneaded to obtain a printing paste.

[0045]

The dyestuffs and dyestuff mixtures according to the invention surprisingly offer distinct advantages in terms of build-up and exhaustion properties compared to similar dyestuffs of EP-A-43,795. High color depths can be obtained with them and they are more economical. Because they perform a more complete exhaustion of the material to be dyed and cause less pollution of the effluent. Their temperature sensitivity is lower, ie
Variations in color depth due to variations in dyeing temperature are smaller. They dye even when the dyeing time is shortened and are absorbed by supports such as modified polyesters, polyamides, cellulose triacetates and secondary cellulose acetates. Yet another advantage is that they are C.I. because of their high color depth and their particularly sharp shades. I. It is a suitable alternative to Disperse Red 60 and has substantial cost advantages over the latter dyes. As a result of their fastness to light, which is excellent even at elevated temperatures and humidity, they are also very suitable for dyeing automotive cover fabrics, optionally in the abovementioned mixtures.

Overall, the dyestuffs and dyestuff mixtures according to the invention therefore offer, compared to the prior art, unexpected and substantial advantages in practical applications.

[0047]

EXAMPLES The present invention will be described in more detail below with reference to examples. The indicated percentages are weight percentages.

Example 1 Formula IIa

[0049]

[Chemical 11] 62.5 g of the dye precursor represented by the following formula was added to a suspension consisting of 100 ml of dimethyl sulfoxide, 2.1 g of sodium cyanide and 7.1 g of copper (I) cyanide.
Introduced at 0-75 ° C. and the mixture at this temperature 3
Stir for 0 minutes. The temperature is then raised to 110 ° C. for 30 minutes, then the batch is slowly stirred until it has cooled, the product is suction filtered, washed with 45 ml of dimethylsulfoxide, 7.5% aqueous ammonia solution and water and reduced pressure. Dry down. In this way, the formula Ia

[0050]

[Chemical 12] 38.2 g of the dyestuff represented by
It has an absorption maximum of and dissolves in o-dichlorobenzene to give a red color.

0.6 g of the dye thus obtained is added to 200 g of water.
Add to 0 g in a finely dispersed form with stirring. Bring the dispersion to pH 4.5 with acetic acid and sodium acetate,
Then 2.0 g of a commercially available dispersant based on naphthalenesulfonic acid / formaldehyde condensation product is added.

Polyester fabric 100 based on polyethylene glycol terephthalate was added to the dyeing liquor thus obtained.
g and dye the fabric at 130 ° C. for 45 minutes. Subsequent rinsing, reductive post-treatment with 0.2% sodium dithionite solution at 70-80 ° C. for 15 minutes, rinsing and drying gave high color strength and very good coloristic properties, A red dyeing is obtained which has very good fastness to light and fastness to dry heat fixation.

Example 2 The procedure described in Example 1 is repeated. However, 62.5 g of the dye precursor represented by the formula IIa is added to the formula IIb.

[0054]

[Chemical 13] 30.1 g of the dye precursor of formula and formula IIc

[0055]

[Chemical 14] Replaced by a mixture of 29 g of the dye precursor of formula Ib

[0056]

[Chemical 15] And a dye of formula Ic

[0057]

[Chemical 16] 44 g of a mixture of dyes of the formula The mixture is
It also dissolves in o-dichlorobenzene to give a red color.

C. I. 1.3 g of a commercially available powder preparation of Dispersion Yellow 42, C.I. I. 1 g of a commercially available powder preparation of Dispersion Blue 27 and 0.1 g of the above dye mixture are added to 2000 g of water.
While stirring. Sodium acetate 4 in the dispersion
g, the mixture is brought to pH 5 with acetic acid and 4 g of a commercial leveling agent based on the linear anionic polycondensation product and 3 g of a commercial UV absorber based on benzotriazole are added. The dye liquor thus obtained contains 100 parts of an automobile cover fabric based on polyethylene glycol terephthalate.
g and dye the fabric at 130 ° C. for 1 hour. Subsequent rinsing, reductive post-treatment, rinsing and drying give brown dyeings having excellent lightfastness.

Example 3 15 g of the dye represented by the formula Ic is finely divided,
45 g of carob seed powder, 6 g of sodium 3-nitrobenzenesulfonate and 3 g of citric acid per 100 g
It is mixed with the printing paste containing. Polyester is printed using this printing paste, and after printing the printing fabric, 1.
Steaming at 5 gauge pressure for 15 minutes, washing with soap, rinsing and drying gives a bluish red print with high color strength and excellent fastness.

Further dyes according to the invention are listed in Table I below, and dye mixtures according to the invention are listed in Table II. They likewise give red dyeings and prints on polyesters and also have very good color properties.

The hue on polyester is defined as follows: 1 = bluish red 2 = red 3 = bright red

[0062]

[Table 1]

[0063]

[Table 2]

[0064]

[Table 3]

[0065]

[Table 4]

[0066]

[Table 5]

[0067]

[Table 6]

[0068]

[Table 7]

[0069]

[Table 8]

[0070]

[Table 9]

Claims (10)

[Claims] 1. The general formula I: [Wherein X is methyl, chlorine or bromine, R ¹ is ethyl, n-propyl, i-propyl, n-butyl or i-butyl, R ² is (C ₁ -C ₆ ) -alkyl, ( C ₁ -C ₄ ) -Alkoxy-substituted linear (C ₂ -C ₄ ) -alkyl, allyl, phenyl, acetyl or propionyl and R ³ is hydrogen, acetyl or propionyl. ] The monoazo dye represented by. 2. X is bromine or chlorine, R ¹ is ethyl, n-propyl or i-propyl, R ² is (C ₁ -C ₄ ) -alkyl, 2-methoxyethyl, 2-
A monoazo dye according to claim 1 which is ethoxyethyl or allyl and R ³ is hydrogen. 3. The general formula I: [Wherein X is methyl, chlorine or bromine, and R ¹ is methyl, ethyl, n-propyl, i-propyl,
n-butyl or i-butyl, R ² is (C ₁ -C ₆ ) -alkyl, (C ₁ -C ₄ ) -alkoxy substituted linear (C ₂ -C ₄ ) -alkyl, allyl, phenyl , Acetyl or propionyl and R ³ is hydrogen, acetyl or propionyl. ] A mixture of at least two monoazo dyes represented by: 4. The monoazo dye represented by the general formula I is R ¹
4. A mixture according to claim 3, which differs only in the meaning of. 5. A monoazo dye or mixture of C.I. I.
A monoazo dye according to claim 1 and / or 2 and a mixture according to claim 3 and / or 4 which has been recolored with Solvent Orange 63 or a similar dye. 6. One or more monoazo dyes of the general formula I and one or more dyes usually used for dyeing polyester fibers or polyester fiber materials for automobile cover fabrics. Mixture of. 7. The mixture according to claim 6, wherein the dye for dyeing automobile cover fabrics is an azo, disazo, anthraquinone, nitro, naphthalimide or terephthalimide dye. 8. A compound represented by the general formula II: Wherein Hal ¹ and Hal ² are, independently of one another, chlorine or preferably bromine and R ¹ , R ² , R ³
And X are as defined in claim 1. ] The compound represented by the formula] is subjected to a nucleophilic exchange reaction, and the nucleophile used at that time is a cyanide ion A method for producing a monoazo dye represented by the general formula I, wherein 9. A monoazo dye of the general formula I according to any one of claims 1, 2 and 5 or more, or a monoazo dye according to any one of claims 3 to 7 A method of using a mixture for dyeing and printing hydrophobic synthetic materials. 10. The method according to claim 9, wherein the polyester fiber or the polyester fiber material for automobile cover fabric is dyed or printed.